EP0194180A1 - Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel - Google Patents

Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel Download PDF

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Publication number
EP0194180A1
EP0194180A1 EP86400307A EP86400307A EP0194180A1 EP 0194180 A1 EP0194180 A1 EP 0194180A1 EP 86400307 A EP86400307 A EP 86400307A EP 86400307 A EP86400307 A EP 86400307A EP 0194180 A1 EP0194180 A1 EP 0194180A1
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EP
European Patent Office
Prior art keywords
diisocyanate
prepolymer
polyhydroxylated
hydroxyl groups
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86400307A
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English (en)
French (fr)
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EP0194180B1 (de
Inventor
Christian Perotto
Philippe Ragon
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Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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Publication of EP0194180A1 publication Critical patent/EP0194180A1/de
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Publication of EP0194180B1 publication Critical patent/EP0194180B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0075—Shaping the mixture by extrusion
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • the present invention relates to the field of composite pyrotechnic products and in particular to propellants for weapons and their manufacturing processes. More precisely, the invention relates to a new process for the manufacture, without solvent, of pyrotechnic composite products with thermosetting binder, that is to say of pyrotechnic products essentially consisting of an inert thermosetting binder and by at least one pulverulent oxidizing charge. The invention also relates to pyrotechnic products, in particular propellant powders, obtained by the process according to the invention.
  • propellant powders known as "homogeneous” consisting of one or more gelatinized energy bases having, seen in section, a homogeneous appearance, hence their name.
  • homogeneous propellant powders mention may be made of "smoke-free" powders based on nitrocellulose alone or based on a nitrocellulose-nitroglycerine mixture. In order to improve the ballistic performance of these powders, attempts have been made to incorporate therein powdery mineral or organic oxidizing charges.
  • Vulnerability means the fact that these powders can ignite and deflagrate under the effect of an unwanted random physical phenomenon such as the impact of a projectile. Vulnerability is a major defect for powders intended to be loaded on board ships, planes or combat tanks. The development of modern combat machines therefore leads the skilled person to seek out poorly vulnerable propellants.
  • Composite powders with an inert binder consisting mainly of a synthetic resin and an inorganic or organic oxidizing charge have been found to be significantly less vulnerable than homogeneous or composite powders with an energy binder.
  • these powders must, in order to present the necessary energy during ignition, contain very high charge rates, often close to 80% of the total weight of the powder.
  • Composite powders with an inert binder thus have the characteristic, compared to other composite materials, of actually containing very little binder relative to the pulverulent filler.
  • thermoplastic binders of synthetic origin usable in composite pyrotechnic products can be classified, like any resin, into thermoplastic binders and thermosetting binders. It is, of course, first of all towards the use of thermoplastic binders that the skilled person has turned, these binders allowing mechanical work at temperature of the product to give it the desired geometry.
  • European patent application 0036481 thus describes a process for manufacturing composite explosives with a thermoplastic binder.
  • the composite products with a thermoplastic binder described in this patent are not entirely satisfactory insofar as their geometry is too sensitive to thermal variations.
  • thermosetting binders such as polyurethane binders or three-dimensional polyesters, allowing, after complete polymerization of the resin, to definitively freeze the geometry of the grain of powder.
  • the manufacture on an industrial scale of such powders is however very difficult because on the one hand that the thermosetting resins have a limited “pot life” (the term “pot life” means the period during polymerization of the resin during which the latter can be worked as a plastic) and on the other hand because of the high loading rate in composite powders, the binder must already have good mechanical strength at the time of extrusion to ensure the cohesion of the propellant paste.
  • thermosetting binders To overcome these drawbacks in the context of the use of thermosetting binders, those skilled in the art have sought to work in the presence of solvents as described for example in French patents 2,268,770 and 2,488,246. These techniques are however '' a complex and costly implementation which is not satisfactory on an industrial scale.
  • This technique which has been widely described, for example in French patents 2 109 102, 2 196 998, 2 478 623 and 2 491 455, may be suitable for the manufacture of solid composite propellants for rocket or rocket engines, or even for the making composite explosives for machine heads which are most often used in the form of large diameter products, but prove to be ill-suited to the industrial manufacture of large composite powders and totally unsuitable for the industrial manufacture of composite powders of small diameters and more generally of small diameter composite pyrotechnics.
  • the object of the present invention is precisely to propose such a method.
  • the invention also relates to composite pyrotechnic products such as propellants for weapons, propellants, explosives obtained by the process according to the invention.
  • the invention relates in particular to powders in which the binder is obtained by reaction of a hydroxytelechelic polybutadiene having an average functionality in OH hydroxyl groups close to 2.3 on a diisocyanate and the energy charge of which consists of hexogen.
  • the invention thus allows a person skilled in the art to have an industrial process for manufacturing solvent-free composite pyrotechnic products and in particular composite propellant powders, having an inert thermosetting binder.
  • the choice of the functionality of the polyhydroxylated prepolymer in fact gives the resulting polyurethane the thermosetting character.
  • the particular operating mode retained within the framework of the invention makes it possible, at the end of the first step, to have a partially polymerized paste having at this stage certain plastic properties making it extrudable including in small diameters, in particular after addition of the additional amount of diisocyanate.
  • the invention therefore relates to a process for manufacturing composite pyrotechnic products, and in particular composite propellant powders, consisting mainly on the one hand of an inert thermosetting binder and on the other hand of at least one organic or mineral energy charge.
  • the inert thermosetting binder usable in the context of the present invention is a polyurethane binder obtained by reaction of a polyhydroxylated prepolymer with a diisocyanate.
  • the polyhydroxylated prepolymer preferably liquid, has, and this is an essential characteristic of the invention, an average functionality in OH hydroxyl groups greater than 2 and less than 3, preferably close to 2.3.
  • Such a prepolymer must be constituted by a mixture of hydroxytelechelic polyfunctional prepolymers, but the final functionality of the prepolymer must not be obtained by adding to an essentially difunctional prepolymer of short tri or tetrafunctional polyols with a molar mass of less than 400 as by for example trimethylol ethane, trimethylol propane, or tetramethylol methane, contrary to what is often practiced in the industry of thermosetting polyurethane resins.
  • Said polyhydroxylated prepolymer must moreover have a weight average molecular weight of between 2000 and 5000 and preferably close to 4000.
  • the preferred polyhydroxylated prepolymers in the context of the present invention are mixtures essentially consisting of polyhydroxylated polybutadienes.
  • Said polyurethane binder is obtained by reaction of said polyhydroxylated prepolymer with a diisocyanate.
  • diisocyanate it is possible to use the aliphatic, cycloaliphatic or aromatic diisocyanates usually used in the manufacture of pyrotechnic compositions using a polyurethane binder.
  • the diisocyanates preferred in the context of the present invention are chosen from the group consisting of toluene-2,4 diisocyanate, toluene-2,6 diisocyanate, methyl-1 cyclohexane-2,4 diisocyanate, methyl-1 cyclohexane- 2.6 diisocyanate, dicyclohexylmethane-4,4 'diisocyanate, isophorone diisocyanate, hexane-1,6 diisocyanate, trimethyr2,2,4,4hexane-1,6 diisocyanate.
  • the aliphatic or cycloaliphatic diisocyanates will preferably be chosen from the above list.
  • the polyhydroxylated prepolymer and the diisocyanate must have rheological properties allowing processing without solvent. Preferably they are liquid.
  • Polyurethane binder audit is mixed with at least one organic or mineral energy charge.
  • the mineral energy charge it is possible to use the charges chosen from the group consisting of ammonium nitrate, ammonium perchlorate, alkaline nitrates, alkaline earth nitrates, alkaline perchlorates, alkaline earth perchlorates.
  • organic energy charge it is possible to use the nitro organic compounds known as energy compounds and in particular cyclotrimethylene trinitramine (hexogen), cyclotetramethylene tetranitramine (octogen), pentaerithritol tetra-nitrate (pentrite), triaminoguanidine nitrate.
  • the ratio between the weight of energy charge relative to the weight of polyurethane binder is preferably close to 4.
  • the pyrotechnic products according to the invention generally contain the usual additives known to those skilled in the art and specific to the final application for which the said products are intended, such as in particular plasticizers, agents wetting agent, antioxidant agents, anti-glow agents, anti-corrosion agents, combustion catalysts, etc.
  • the process for manufacturing composite pyrotechnic products according to the invention is further characterized by the fact that one operates in three distinct stages.
  • said polyhydroxylated polymer is preferably mixed with said energy charge in a kneader in the presence of the desired additives as described above and with an amount of diisocyanate of between 50% and 90% by weight of the stoichiometric amount necessary for the complete polymerization of all the hydroxyl groups OH of said polyhydroxylated prepolymer.
  • the condensation reaction of the NCO isocyanate groups on the OH hydroxyl groups is carried out so as to obtain a partially polymerized paste. It is at this first stage that the importance of the conditions of functionality previously stated about the polyhydroxylated prepolymer and diisocyanate.
  • the polyhydroxylated prepolymers having a functionality in OH hydroxyl groups of between 2 and 3 obtained by mixing di-functional prepolymers and trifunctional prepolymers to the exclusion of any short tri or tetrafunctional polyol, statistically have two OH reactive hydroxyl groups which are more reactive than the third group used to provide additional functionality.
  • an amount of diisocyanate representing only 50% to 90% by weight of the total stoichiometric amount of diisocyanate necessary for the complete polymerization of all the hydroxyl groups OH of said prepolymer, the diisocyanate will react preferentially with the two OH groups the most reactive of the prepolymer according to an essentially linear polymerization.
  • the amount of diisocyanate introduced is between 70% and 80% by weight of said stoichiometric amount and the condensation reaction of the isocyanate NCO groups on the OH hydroxyl groups is carried out at a temperature between 50 and 80 ° C.
  • a second step the mixture of diisocyanate necessary to reach said stoichiometric quantity necessary for polymerization is mixed, preferably in a kneader-extruder, or in a twin-screw extruder, with the partially polymerized paste obtained at the end of the first step. complete with all the hydroxyl groups OH of said prepolymer, after homogenization, the pasty mixture thus obtained is extruded to the desired geometry.
  • the pasty mixture obtained in this second step while being of thermosetting nature is almost non-reactive at room temperature or even at slightly temperature higher than room temperature.
  • this pasty mixture has both sufficient plastic properties to be able to be extruded, even in small diameters, through dies comprising pins and already sufficiently mechanical strength to maintain, after extrusion, its shape pending final crosslinking hot which is the third step of the method according to the invention.
  • a third step therefore, the condensation reaction of the NCO isocyanate groups added during the second step with the hydroxyl OH groups still free of the prepolymer is completed by hot cooking.
  • This cooking which is preferably carried out at a temperature between 50 ° C. and 80 ° C., makes it possible to complete the three-dimensional crosslinking of the thermosetting binder and to definitively freeze the chemical structure of the pyrotechnic product obtained.
  • the product obtained can undergo the usual finishing treatments required for its final application after having possibly been put into its final form by machining or cutting.
  • the method according to the invention thus makes it possible to obtain composite pyrotechnic products with thermosetting binder without the use of solvent and by being freed from the disadvantages presented by the previous methods using mixtures having a limited pot life.
  • the method according to the invention is in particular well suited to obtaining composite propellant powders with thermosetting binder for weapons, and in particular for small caliber weapons.
  • the method according to the invention makes it possible in particular to easily obtain cylindrical composite propellant powders having the conventional geometries with one hole, seven holes or nineteen holes used in the small and medium caliber weapons.
  • preferred powders are the powders obtained using as prepolymer a polyhydroxylated polybutadiene having an average functionality in OH hydroxyl groups close to 2.3 and using as filler hexogen.
  • Particularly preferred powders are those obtained by using in addition as diisocyanate a diisocyanate chosen from the group consisting of aromatic diisocyanates and in particular toluene diisocyanate.
  • the method according to the invention is also applicable to obtaining composite propellants with thermosetting binder or composite explosives with thermosetting binder.
  • the use of the method according to the invention, in this context, is particularly advantageous in the cases where it is desired to obtain composite propellants or extruded composite explosives of small diameter.
  • a granular powder in cylindrical geometry with 7 channels was produced according to the process which is the subject of the present invention.
  • the composition of the powder is as follows:
  • the polybutadiene used has a weight average molecular weight of 4000 and an average functionality in OH hydroxyl groups of 2.3, while the polyether used has a weight average molecular weight of 2000 and an average functionality in OH hydroxyl groups of 3.
  • Second step the pre-crosslinked dough, cut into a parallelepiped shape, is introduced into the tank of a mixer-extruder. After 10 minutes of mixing, the additional crosslinking agent is produced and then homogenized at 30 ° C.
  • the dough is extruded after 20 minutes of mixing, through three dies which present the final geometry of the powder.
  • Third step post baking in an oven is carried out on long extruded strands, for two days at 60 ° C.
  • the grain cutting is then carried out, making it possible to have a directly usable bulk powder.
  • a granular powder in cylindrical geometry with 7 channels was produced according to the process which is the subject of the present invention.
  • the composition is the same as in Example 1 except the nature of the nitramine, the hexogen being replaced by octogen (0-100 ⁇ ).
  • a powder in grains of cylindrical geometry comprising 7 channels was produced according to the process which is the subject of the present invention.
  • the composition of the powder is as follows:
  • the polybutadiene and the polyether are those used in Example 1.
  • the process used for the implementation of this composition is the same as that described in Example 1 except in the first step where the NCO / OH ratio was equal at 0.75.
  • a powder in grains of cylindrical geometry comprising 7 channels was produced according to the process which is the subject of the present invention.
  • composition of the powder is as follows:
  • the polybutadiene and the polyether are those used in Example 1.
  • the process used for the implementation of this composition is the same as that described in Example 1 except in the first step where the NCO / OH ratio was equal at 0.70.
  • a powder in grains of cylindrical geometry comprising 7 channels was produced according to the process which is the subject of the present invention.
  • composition of the powder is as follows:
  • the hydroxytelechelic polyether has a weight average molar mass of 2800 and a functionality in OH hydroxyl groups close to 2, the polyether triol has a weight average molecular weight of 2000 and a functionality in OH hydroxyl groups equal to 3.
  • a powder in grains of cylindrical geometry comprising 7 channels was produced according to the process which is the subject of the present invention.
  • composition of the powder is as follows:
  • the hydroxytelechelic polyester has a weight-average molar mass of 3200 and a functionality in OH hydroxyl groups equal to 2.4, the polyether triol is the same as that used in Example 6.
  • a powder in cylindrical geometry grains comprising seven channels was produced according to the process which is the subject of the present invention.
  • composition of the powder is as follows:
  • the hydroxytelechelic polycarbonate has a weight-average molar mass of 3000 and a functionality in OH hydroxyl groups close to 2.7.
  • Hollow strands were made of composite propellant for the production of very short combustion duration loads according to the process of the present invention.
  • composition of the propellant is as follows:
  • the hydroxytelechelic polybutadiene is the same as that used in Example 1.
  • the manufacturing process used is the same as that described in Example 1 except in the first step where the NCO / OH ratio was equal to 0.75.
  • the load consists of 31 identical strands which are embedded in an inert sole.
  • composition of this explosive is as follows:
  • polyester and polyether are the same as those used in Example 7.
  • the process used for the implementation of this composition is the same as that described in Example 1, except in the first step where the NCO / OH was equal to 0.84.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
EP86400307A 1985-02-27 1986-02-13 Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel Expired EP0194180B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8502796 1985-02-27
FR8502796A FR2577919B1 (fr) 1985-02-27 1985-02-27 Procede de fabrication sans solvant de produits pyrotechniques composites a liant thermodurcissable et produits ainsi obtenus, notamment poudres propulsives composites

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EP0194180A1 true EP0194180A1 (de) 1986-09-10
EP0194180B1 EP0194180B1 (de) 1989-05-03

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EP86400307A Expired EP0194180B1 (de) 1985-02-27 1986-02-13 Verfahren zur lösungsmittelfreien Herstellung von Zusammensetzungen für pyrotechnische Erzeugnisse mit wärmehärtbarem Bindemittel

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US (1) US4657607A (de)
EP (1) EP0194180B1 (de)
JP (1) JPS61201687A (de)
KR (1) KR900000084B1 (de)
AU (1) AU577250B2 (de)
CA (1) CA1256702A (de)
DE (1) DE3663134D1 (de)
FR (1) FR2577919B1 (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251606A2 (de) * 1986-06-21 1988-01-07 Freeman Chemicals Limited Polymers Division Schutz einer gefährlichen Substanz
EP0327673A1 (de) * 1988-02-10 1989-08-16 Contec- Chemieanlagen Gmbh Giess- und/oder pressbare Gasgeneratortreibstoffe
DE19528052A1 (de) * 1994-07-29 1996-02-01 Poudres & Explosifs Ste Nale Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von pyrotechnischen Composit-Produkten
EP0718257A1 (de) * 1994-12-22 1996-06-26 Societe Nationale Des Poudres Et Explosifs Verfahren zur kontinuierlichen Herstellung von Siliconharz-gebundenen pyrotechnischen Ladungen und Zusammensetzung zur Verwendung in einem solchen Verfahren
FR2746389A1 (fr) * 1982-05-28 1997-09-26 United Kingdom Government Propergol composite, charge propulsive et leurs procedes de fabrication
EP0853603A1 (de) * 1995-10-03 1998-07-22 Atlantic Research Corporation Schnellhärtendes Bindemittelsystem mit Hydroxylendgruppen enthaltende, geformte, gaserzeugende Zusammensetzungen und Verfahren zur Herstellung
EP0959058A1 (de) * 1998-05-20 1999-11-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Hydrazin-Nitroform enthaltende feste Hochleistungstreibstoffe
WO1999062846A1 (en) * 1998-06-01 1999-12-09 Alliant Techsystems Inc. Non-energetic binder with a reduced energetic plasticizer content for energetic compositions
FR2893613A1 (fr) * 2005-11-24 2007-05-25 Eurenco France Sa Procede bicomposant semi-continu perfectionne d'obtention d'un chargement explosif composite a matrice polyurethanne
WO2015075328A1 (fr) 2013-11-22 2015-05-28 Herakles Produit pyrotechnique composite a liant réticule et son procédé de préparation
WO2015075327A1 (fr) 2013-11-22 2015-05-28 Herakles Produit pyrotechnique composite a liant non reticule et son procede de preparation
FR3072676A1 (fr) * 2017-10-24 2019-04-26 Arianegroup Sas Procede de fabrication d'un produit pyrotechnique composite

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US5500060A (en) * 1986-07-04 1996-03-19 Royal Ordnance Plc Energetic plasticized propellant
US5320043A (en) * 1990-10-17 1994-06-14 Snpe Inc. Low-vulnerability explosive munitions element including a multicomposition explosive charge, and method for obtaining a blast and/or bubble effect
FR2668146B1 (fr) * 1990-10-17 1993-10-22 Poudres Explosifs Ste Nale Element peu vulnerable de munition explosive comportant un chargement explosif multi-composition et procede d'obtention d'un effet de souffle et/ou de bulles.
GB2258656B (en) * 1991-08-15 1994-01-12 Albright & Wilson Processing of powder
DE4200743C2 (de) * 1991-09-18 1994-04-07 Wasagchemie Sythen Gmbh Verfahren und Vorrichtung zur Verringerung der Korngröße von kristallinem Explosivstoff
FR2688498B1 (fr) * 1992-03-11 1994-05-06 Poudres Explosifs Ste Nale Poudre propulsive a faible vulnerabilite sensible a l'allumage.
FR2749008B1 (fr) * 1996-05-23 1998-06-26 Poudres & Explosifs Ste Nale Procede continu de fabrication sans solvant de produits pyrotechniques composites thermodurcissables
US6802533B1 (en) 2000-04-19 2004-10-12 Trw Inc. Gas generating material for vehicle occupant protection device
FR2835519B1 (fr) * 2002-02-01 2004-11-19 Poudres & Explosifs Ste Nale Procede bicomposant semi-continu d'obtention d'un chargement explosif composite a matrice polyurethanne
JP2006151791A (ja) * 2004-11-01 2006-06-15 Asahi Kasei Chemicals Corp ニトラミン発射薬
JP4131748B1 (ja) * 2008-01-16 2008-08-13 株式会社タイホーコーザイ 燃料添加剤
US8575074B2 (en) 2011-06-06 2013-11-05 Los Alamos National Security, Llc Insensitive explosive composition and method of fracturing rock using an extrudable form of the composition
KR101974125B1 (ko) * 2018-01-08 2019-08-23 주식회사 한화 고체 추진제 조성물 및 이를 제조하는 방법

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FR2225979A5 (en) * 1969-12-24 1974-11-08 France Etat Highly explosive composite contg. crosslinked polyurethane binder - and nitro org cpds., with high explosive content
FR2427317A1 (fr) * 1978-05-30 1979-12-28 Hercules Inc Liant reticule pour composition propulsive a double base reticulee
US4267132A (en) * 1974-05-28 1981-05-12 The United States Of America As Represented By The Secretary Of The Navy Method for high strength double base solventless gun propellant
GB2073764A (en) * 1980-03-20 1981-10-21 Hercules Inc Crosslinked Propellants
US4456493A (en) * 1983-04-11 1984-06-26 Thiokol Corporation Low vulnerability gun propellant

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US4110135A (en) * 1976-11-11 1978-08-29 Thiokol Corporation Control of cure rate of polyurethane resin based propellants
US4184031A (en) * 1976-11-11 1980-01-15 Thiokol Corporation Control of cure rate of polyurethane resins
US4196129A (en) * 1977-01-21 1980-04-01 California Institute Of Technology Prepolymer dianhydrides
US4555277A (en) * 1985-01-29 1985-11-26 The United States Of America As Represented By The Unites States Department Of Energy Extrusion cast explosive

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
FR2225979A5 (en) * 1969-12-24 1974-11-08 France Etat Highly explosive composite contg. crosslinked polyurethane binder - and nitro org cpds., with high explosive content
US4267132A (en) * 1974-05-28 1981-05-12 The United States Of America As Represented By The Secretary Of The Navy Method for high strength double base solventless gun propellant
FR2427317A1 (fr) * 1978-05-30 1979-12-28 Hercules Inc Liant reticule pour composition propulsive a double base reticulee
GB2073764A (en) * 1980-03-20 1981-10-21 Hercules Inc Crosslinked Propellants
US4456493A (en) * 1983-04-11 1984-06-26 Thiokol Corporation Low vulnerability gun propellant

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2746389A1 (fr) * 1982-05-28 1997-09-26 United Kingdom Government Propergol composite, charge propulsive et leurs procedes de fabrication
EP0251606A3 (de) * 1986-06-21 1990-10-17 Freeman Chemicals Limited Polymers Division Schutz einer gefährlichen Substanz
EP0251606A2 (de) * 1986-06-21 1988-01-07 Freeman Chemicals Limited Polymers Division Schutz einer gefährlichen Substanz
EP0327673A1 (de) * 1988-02-10 1989-08-16 Contec- Chemieanlagen Gmbh Giess- und/oder pressbare Gasgeneratortreibstoffe
DE19528052C2 (de) * 1994-07-29 2003-02-27 Poudres Et Explosifs Paris Soc Verfahren zur kontinuierlichen, lösungsmittelfreien Herstellung pyrotechnischer Composit-Produkte
DE19528052A1 (de) * 1994-07-29 1996-02-01 Poudres & Explosifs Ste Nale Kontinuierliches Verfahren zur lösungsmittelfreien Herstellung von pyrotechnischen Composit-Produkten
FR2728562A1 (fr) * 1994-12-22 1996-06-28 Poudres & Explosifs Ste Nale Procede de fabrication en continu de chargements pyrotechniques a liant silicone et compositions susceptibles d'etre mises en oeuvre par ce procede
EP0718257A1 (de) * 1994-12-22 1996-06-26 Societe Nationale Des Poudres Et Explosifs Verfahren zur kontinuierlichen Herstellung von Siliconharz-gebundenen pyrotechnischen Ladungen und Zusammensetzung zur Verwendung in einem solchen Verfahren
EP0853603A1 (de) * 1995-10-03 1998-07-22 Atlantic Research Corporation Schnellhärtendes Bindemittelsystem mit Hydroxylendgruppen enthaltende, geformte, gaserzeugende Zusammensetzungen und Verfahren zur Herstellung
EP0853603A4 (de) * 1995-10-03 2000-11-22 Atlantic Res Corp Schnellhartendes bindemittelsystem mit hydroxylendgruppen fuer gaserzeugende zusammensetzungen
EP0959058A1 (de) * 1998-05-20 1999-11-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Hydrazin-Nitroform enthaltende feste Hochleistungstreibstoffe
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EP1790626A1 (de) * 2005-11-24 2007-05-30 Eurenco France Semikontinuierliches Verfahren zur Herstellung einer explosiven Komposit-Ladung mit einer Polyurethanmatrix durch Verwendung von zwei Komponenten
WO2007060365A2 (fr) * 2005-11-24 2007-05-31 Eurenco France Procede bicomposant semi-continu perfectionne d'obtention d'un chargement explosif composite a matrice polyurethanne
WO2007060365A3 (fr) * 2005-11-24 2007-08-02 Eurenco France Procede bicomposant semi-continu perfectionne d'obtention d'un chargement explosif composite a matrice polyurethanne
NO20082110L (no) * 2005-11-24 2008-05-07 Eurenco France Halvkontinuerlig fremgangsmåte for å oppnå en sammensatt sprengladning med polyuretanmatriks
US7887651B1 (en) 2005-11-24 2011-02-15 Eurenco Semi-continuous two-component method for obtaining a composite explosive charge with polyurethane matrix
NO341597B1 (no) * 2005-11-24 2017-12-11 Eurenco France Halvkontinuerlig fremgangsmåte for å oppnå en sammensatt sprengladning med polyuretanmatriks
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WO2015075327A1 (fr) 2013-11-22 2015-05-28 Herakles Produit pyrotechnique composite a liant non reticule et son procede de preparation
FR3072676A1 (fr) * 2017-10-24 2019-04-26 Arianegroup Sas Procede de fabrication d'un produit pyrotechnique composite
EP3476821A1 (de) * 2017-10-24 2019-05-01 Arianegroup Sas Herstellungsverfahren eines pyrotechnischen verbundprodukts

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CA1256702A (en) 1989-07-04
DE3663134D1 (en) 1989-06-08
FR2577919B1 (fr) 1987-02-20
AU577250B2 (en) 1988-09-15
AU5414886A (en) 1986-09-04
KR860006423A (ko) 1986-09-11
US4657607A (en) 1987-04-14
KR900000084B1 (ko) 1990-01-19
FR2577919A1 (fr) 1986-08-29
JPH0432038B2 (de) 1992-05-28
EP0194180B1 (de) 1989-05-03
JPS61201687A (ja) 1986-09-06

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